Gradient nanoparticle-carbon allotrope-polymer composite material

ABSTRACT

A shock wave attenuating material ( 100 ) includes a substrate layer ( 104 ). A plurality ( 110 ) of shock attenuating layers is disposed on the substrate layer ( 104 ). Each of the plurality ( 110 ) of shock attenuating layers includes a gradient nanoparticle layer ( 114 ) including a plurality of nanoparticles ( 120 ) of different diameters that are arranged in a gradient from smallest diameter to largest diameter and a graphitic layer ( 118 ) disposed adjacent to the gradient nanoparticle layer. The graphitic layer ( 118 ) includes a plurality of carbon allotrope members ( 128 ) suspended in a matrix ( 124 ).

RELATED APPLICATIONS

This application claims the benefit of U.S. patent application Ser. No. 13/880,270 ('270 Application and now U.S. Pat. No. 10,926,513) filed Apr. 18, 2013, and completed, for purposes of 35 U.S.C. § 371(c), on Jun. 25, 2013, wherein the '270 Application is a U.S. National Stage of PCT application PCT/US2011/056696 filed Oct. 18, 2011, the entirety of these applications which are incorporated by reference. This application also claims the benefit of U.S. Provisional Patent Application Ser. Nos. 61/394,066, filed Oct. 18, 2010, 61/411,494, filed Nov. 9, 2010, and 61/477,674, filed Apr. 21, 2011, the entirety of each of which is hereby incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to protective materials and, more specifically, to a material that diminishes the effect of a shock wave.

2. Description of the Related Art

Material designs for handling the impact of an external stimulus, such as a blast, as shock wave or projectiles, include, for example, woven fabrics, ceramic materials, and composite systems. Kevlar®, Zylon®, Armos®, Spectra® are commercially available fabrics made from high-strength fibers. Another material is ballistic steel, which is comprised of hardened high tensile steel, woven into fiber form. Further, boron carbide can be used as a material, for example, in the production of body armor.

Ceramic materials, in particular ceramic metal composites have found utility in light weight body armor.

Existing systems attempt to attenuate shock waves by presenting a high mass material between the source of the shock wave and the thing being protected. The high mass material absorbs some of the shock wave energy, thereby resulting in a shock wave of decreased amplitude. However, while the wave's amplitude may be decreased, it is only decreased by a certain amount and my still do considerable damage.

Therefore, there is a need for a material that disrupts a shock wave, thereby lessening its effect.

SUMMARY OF THE INVENTION

The disadvantages of the prior art are overcome by the present invention which, in one aspect, is a shock wave attenuating material that includes a substrate layer. A plurality of shock attenuating layers is disposed on the substrate layer. Each of the plurality of shock attenuating layers includes a gradient nanoparticle layer including a plurality of nanoparticles of different diameters that are arranged in a gradient from smallest diameter to largest diameter and a graphitic layer disposed adjacent to the gradient nanoparticle layer. The graphitic layer includes a plurality of carbon allotrope members suspended in a matrix.

In another aspect, the invention is a helmet that includes a helmet member configured to be worn by a user. A plurality of shock attenuating layers is applied to the helmet member. Each shock attenuating layer includes a gradient nanoparticle layer including a plurality of nanoparticles of different diameters that are arranged in a gradient from smallest diameter to largest diameter; and a graphitic layer disposed adjacent to the gradient nanoparticle layer, the graphitic layer including a plurality of carbon allotrope members suspended in a matrix.

In another aspect, the invention is an armor unit that includes a structural element, an armor plate and a plurality of shock attenuating layers. The plurality of shock attenuating layers is disposed in a predetermined relationship with at least one of the structural element and the armor plate. Each shock attenuating layer includes a gradient nanoparticle layer including a plurality of nanoparticles of different diameters that are arranged in a gradient from smallest diameter to largest diameter; and a graphitic layer disposed adjacent to the gradient nanoparticle layer, the graphitic layer including a plurality of carbon allotrope members suspended in a matrix.

In yet another aspect, the invention is a personal body armor unit that includes a ceramic plate, a high mass member and a nanoparticle shock wave attenuating material layer. The high mass member is disposed adjacent to the ceramic plate. The nanoparticle shock wave attenuating material layer is disposed on the high mass member.

The nanoparticle shock wave attenuating material layer can be disposed between the high mass member and the ceramic plate. Similarly, the nanoparticle shock wave attenuating material layer can be disposed outside of the high mass member or the ceramic plate or both. It is understood that any combination of these configurations fall within the scope of the invention.

These and other aspects of the invention will become apparent from the following description of the preferred embodiments taken in conjunction with the following drawings. As would be obvious to one skilled in the art, many variations and modifications of the invention may be effected without departing from the spirit and scope of the novel concepts of the disclosure.

BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWINGS

FIG. 1 is a schematic diagram of one embodiment of a shock wave attenuating material.

FIG. 2A is a schematic diagram of one embodiment of a gradient nanoparticle layer.

FIG. 2B is a schematic diagram of one embodiment of a graphitic layer.

FIG. 3 is a schematic diagram of the embodiment shown in FIG. 1, demonstrating shock wave attenuation.

FIG. 4 is a schematic diagram of one embodiment of a helmet.

FIG. 5 is a schematic diagram of one embodiment of an armor unit.

FIG. 6 is a schematic diagram of one embodiment of a body armor unit.

FIG. 7 is a schematic diagram of one embodiment of a body armor unit.

FIG. 8 is a schematic diagram of one embodiment of a body armor unit.

DETAILED DESCRIPTION OF THE INVENTION

A preferred embodiment of the invention is now described in detail. Referring to the drawings, like numbers indicate like parts throughout the views. Unless otherwise specifically indicated in the disclosure that follows, the drawings are not necessarily drawn to scale. As used in the description herein and throughout the claims, the following terms take the meanings explicitly associated herein, unless the context clearly dictates otherwise: the meaning of “a,” “an,” and “the” includes plural reference, the meaning of “in” includes “in” and “on.”

U.S. patent application Ser. No. 12/672,865 (U.S. Patent Publication 2011/0212320) discloses a gradient nanoparticle composite material and a method of making a gradient nanoparticle composite material and is hereby incorporated by reference.

As shown in FIG. 1, one embodiment of a shock wave attenuating material 100 includes a substrate layer 104 and a plurality 110 of shock attenuating layers disposed on the substrate layer. Each of the plurality 110 of shock attenuating layers includes a gradient nanoparticle layer 114 and a graphitic layer 118 disposed adjacent to the gradient nanoparticle layer 114. In a typical embodiment, the shock wave attenuating material 100 would include at least 10 gradient nanoparticle layers 114 alternating with at least 10 graphitic layers 118 (while only three are shown in FIG. 1 for the sake of simplicity).

As shown in FIG. 2A, each nanoparticle layer 114 includes a plurality of nanoparticles 120 of different diameters (at least two different diameters) that are arranged in a gradient from smallest diameter to largest diameter. The specific orientation of the gradient (smallest to largest vs. largest to smallest) depends on the specific application for which the material is being used.

As shown in FIG. 2B, the graphitic layer 118 includes a plurality of carbon allotrope members 128 suspended in a matrix 124. The carbon allotrope members 128 can include graphene sheets, carbon nanotubes, fullerenes, functionalized graphene sheets, functionalized carbon nanotubes, and functionalized fullerenes.

Depending upon any transparency requirement, the nature of the substrate may be varied. Two potential substrates are polycarbonate and carbon fiber composites/laminates. In fact, a thicker (yet still transparent) polymer-graphene composite layer may be employed directly as the substrate. The gradient structure may be any of those shown, for example, in U.S. Patent Publication US-2011-0212320-A1, which is incorporated herein by reference, as well as others built up from the same principles. One embodiment of a gradient structure has a total thicknesses of the order of 5-10 .μm which can then be repeated as many times as required.

A fullerene layer may be directly deposited by coating, from a toluene solution, onto the gradient structure in thicknesses as small as a monolayer. Similarly, nanotubes and graphene or graphene oxide sheets may be coated from suspensions in organic solvents such as chloroform. However, these two allotropes may also be (preferentially) deposited as polymer composites. The use of a polymer composite provides additional structural integrity to the overall coating and, more importantly, provides additional impact regions for the generation of partially reflected shock waves and will further reduce the overall passage of the shock energy from the impact site to the protection site. Carbon allotrope members 128 can be functionalized as a graphene oxide. Similarly, nanotubes and fullerenes can be functionalized with carboxylic acid, amines, can be hydroxylated or carboxylated.

As shown in FIG. 3, the graphitic layers 118 are of a thickness that is sufficient to reflect at least a portion of a shock wave impinging thereon. The thickness of the graphitic layers 118 will depend on the type of shock wave that the designer desires to protect against. When a shock wave 302 impinges on the material 100, the first gradient nanoparticle layer 114 begins to attenuate the shock wave 304 and the first graphitic layer 118 reflects a portion of the shock wave 306, thereby generating destructive interference with any residual shock wave energy. Successive waves 308 and 312 reflect in a similar fashion to generate reflected waves 310 and 314, which further interfere with residual shock energy.

The carbon or carbon composite layers mark the end of one nanostructure and the start of the next. A significant reduction of the incident shock wave occurs after passage through less than 10 μm of gradient nanoparticles. Stacks or layers of such structures with the carbon and/or carbon composites are interspersed and define the layer or stack limit. The effect, at each carbon interface, will be to create a backward traveling wave causing attenuation of the incident shock wave, as well as a much reduced forward transmitted shock wave, which passes in to the next layer of the structure. A stack of 50 alternating gradient nanoparticle structures (each composed of 30 nanoparticle layers) and composite layers would result in a 1 mm thick coating and significant attenuation of the incident shock wave. Each of these 50 gradient or composite layers is one-fifth the thickness of the typical human hair.

As shown in FIG. 4, the shock wave attenuating material 110 can be part of a helmet 400 or helmet liner. In one embodiment, a helmet 400 includes a helmet member 402 configured to be worn by a user, such as an Enhanced Combat Helmet [ECH] used in military applications. The helmet member 402 could be made from a para-aramid synthetic fiber composite, such as Kevlar®. In other embodiments, the helmet could be of the type used in sports. For example, the shock wave attenuating material 110 could be used in a baseball helmet, a football helmet, a hockey helmet, a bicycling helmet, or the like. The helmet 400 could include an outer shell (such as, e.g., acrylonitrile butadiene styrene), a shock wave attenuating material 110 layer and an inner shell. The helmet 400 could even include an outer shell and several layers of shock wave attenuating material 110 alternating with high mass material layers. The high mass material could include, for example, a high density plastic, a composite, fiber glass, a para-aramid synthetic fiber composite, a vinyl, acrylonitrile butadiene styrene, an acrylic, a metal, or any other material typically used in a helmet. A shock-absorbing foam liner may also be added to the helmet.

As shown in FIG. 5, the shock wave attenuating material 110 can be part of a an armor unit 500, which can include a structural element 502, such as a vehicle panel. An outer armor plate 510, such as a ceramic or composite plate, provides an outer armor surface. The shock wave attenuating material 110 is disposed between the structural element 502 and the armor plate 510. The shock wave attenuating material 110 could also be outside of either the structural element 502 or the armor plate 510 or both. It will be appreciated that any combination of these configurations will fall within the scope of the invention.

As shown in FIG. 6, one embodiment of a body armor assemblage 600, such as an interceptor body armor assemblage (of the type used in the Improved Outer Tactical Vest, Improved Modular Tactical Vest and the US Army and USMC plate carriers). Such an assemblage 600 would include an armor plate 602 (such as a ceramic plate) with a high mass member. Examples of materials suitable for use in the high mass member include: a high density polymer 610 (such as an ultra high molecular weight polyethylene), a para-aramid synthetic fiber composite, a carbon fiber composite, a metal, a ceramic and combinations thereof. The shock wave attenuating material 110 can be applied to the high density polymer 610 on the high density polymer 610 opposite from the armor plate 602 on the side adjacent to the body of the user. This latter application helps solve the problem of backface deformation. As shown in FIG. 7, in one embodiment of a personal body armor assemblage 620, the shock wave attenuating material 110 is disposed between the high density polymer 610 and the armor plate 602. As shown in FIG. 8, multiple layers of shock wave attenuating material 110 may be applied to the armor assemblage 630.

In one application, the shock wave attenuating material 110 can be applied to such devices as soccer shin guards, baseball catchers' chest pads, football shoulder pads, baseball mitts and the like. In can also be applied to such devices as golf clubs and baseball bats to reduce the effects of shock associated with their use.

In some embodiments, the gradient nanoparticle composite material is capable of absorbing an impact of a shock wave that, for example, is produced by an explosion or caused during operation of a device. In some embodiments, the gradient nanoparticle composite material is capable of mitigating and/or remediating one or more secondary blast effects resulting from the explosion.

In some embodiments, the gradient nanoparticle composite material is capable of reacting to and/or interacting with one or more stimuli existing in a blast zone environment. For example, in some embodiments the material can absorb at least a portion of an initial blast impact and/or the over pressure wave resulting from an explosion. In addition, or alternatively, gradient nanoparticle composite material can be designed to mitigate and/or remediate one or more related blast effects resulting from the blast impact itself. Thus, some embodiments can provide a composite material that through intelligent design of the system can not only reduce blast impact with greater efficiency and efficacy, but that can also mitigate and/or remediate one or more secondary blast effects.

In some embodiments, the gradient nanoparticle composite material can provide bomb blast mitigation and/or remediation by reducing the reflective value of the bomb blast by absorption of the bomb blast energy. In some embodiments, the primary mitigating and/or remediating process can be by absorption of the bomb blast shock wave. In some embodiments, the mitigating and/or remediating process can be by absorption of the pre-over pressure wave that precedes the shock wave. Absorption of the shock wave and/or the pre-over pressure wave can occur through one or more mechanisms, including, for example, momentum transfer, destruction of the spatial symmetry of, e.g., the blast wave, plastic deformation, rupture of particles, e.g. filled and unfilled core-shell particles, restitution, and interparticle/interlayer shear.

In some embodiments, the gradient nanoparticle composite material can provide a platform from which a wide variety of blast effects can be mitigated and/or remediated. For example, in a filled-shell material the absorbed energy can be utilized to rupture, e.g., microcapsules to introduce a series or selection of materials or material systems into the blast environment and to thus mitigate and/or remediate the blast effects. In some embodiments, the gradient nanoparticle composite material can provide a relatively light weight material that can be applied to preexisting structures or systems with no deleterious effects on the performance attributes of the pre-existing structure or system.

Some embodiments provide bomb proofing, impact or smart material applications. Examples of bomb proof applications include receptacles and liners (such as in waste receptacles and bags etc.), satellites, helicopters, and high tech devices (computer/hardware casings, cable protection), construction (buildings and their facades), bridges and their structural members, pipes and pipelines (for fossil fuels, conduits, utilities), automotive (door panels, bumpers, dashboards, windshields and windows, undercarriages and roofs), aerospace (interior/exterior of planes), etc. In some embodiments, the gradient nanoparticle composite material can be used in connection with military equipment, structures, vehicles, vessels and crafts for land, sea, and airborne forces to include armored and unarmored vehicles, aircraft, (which includes helicopters and unmanned drones), and nautical vessels such as submarines, ships, boats and the like.

For military and civilian uses, the gradient nanoparticle composite material can be applied as an exterior coating, film, intermediate layer and/or as a panel to pre-existing equipment or, alternatively, can be utilized for forming structural components of the military vehicle, aircraft, or nautical vessel.

The application of gradient nanostructured composites for the attenuation of shock waves is based on the same principles that apply macroscopic granular spheres to create blast walls. Granular materials, especially arranged in a gradient, create mismatching of the solitary wave at each particle contact point and, hence, attenuation of that wave. The effect is a combination of passive and active physical processes: absorption, distortion, and engineered redirection of the shock wave without appreciable heating. In effect, the composite causes destructive interference of the shock wave to attenuate the incident wave. The composite, an ordered structure including selected solid, hollow and filled nanoparticles, may be coated onto a surface (e.g., a protective device, such as a helmet) and may also be produced as a self-supported liner (using plastic containment). Additionally, while the gradient array provides shock attenuation, the material within the filled nanoparticles acts to create an indicator that the user has experienced a shock wave sufficient to cause mild or severe traumatic brain injury while wearing the protective device, such as a helmet. The final product is a lightweight coating that does not change the flexibility of the treated material and which can be made transparent by careful choice of nanoparticle materials. After activation, the protective device may be recoated, if that technology was used in production, or the liner may be replaced, if that approach was employed.

One-dimensional models of a shock wave propagating through a homogeneous or a tapered granular chain demonstrate shock wave attenuation. While three-dimensional structures are too complex for existing modeling systems, the major properties observed for one dimensional calculations are valid in the three-dimensional case. Assuming no elastic effects and no loading, the spheres are simply touching at a single point of contact, the kinetic energy loss is calculated as a function of the change in sphere radius, q, as a wave travels through the spheres, the energy lost per collision in the spheres, E_(L), and the number of spheres, N, in the chain:

$\begin{matrix} {\frac{{KE}_{OUT}}{{KE}_{IN}} = \left\{ \frac{\left\lbrack {{2\left( {1 - q} \right)^{3}} - E_{L}} \right\rbrack^{2}}{{\left( {1 - q} \right)^{3}\left\lbrack {1 + \left( {1 - q} \right)^{3}} \right\rbrack}^{2}} \right\}^{N - 1}} & (1) \end{matrix}$

The values of q and N are fixed by the experiment; the loss term is defined by the ratio of the loading force as two particles come together under the influence of a wave and the unloading forces, as they separate. The decrease in kinetic energy predicted by Equation (1), KE_(OUT)/KE_(IN), is independent of the size of the spheres. The decrease in kinetic energy occurs because each particle absorbs some of the incident energy and that energy remains with the particle. Note that for small values of N, a chain of constant size (q=0) exhibits little loss of kinetic energy. For values of q of the order of 10% and elastic losses of approximately 5%, as much as 80% of the input energy may be absorbed in a chain of 20 spheres. Experimental evidence confirms the theoretical prediction. The large number of nanoparticles in a typical coating provides a large number of the particle to particle contact points required by Equation (1) and also serves to dissipate the kinetic energy surrendered by the incident shock wave without appreciable heating of the coating.

Experimental evidence and theory indicate that the concept and its shock attenuation benefit are independent of particle size. That fact opens the door to using the principles to design nanostructures with a tapered chain-like structure. Such a structure is inherently three-dimensional and beyond the current theoretical models. However, careful consideration indicates that it is best described as a gradient array of nanoparticles; a structure tapered in multiple directions and offering increased attenuation of incoming shock waves. The structure could be built from monolayers of nanoparticles deposited on a substrate beginning with the smallest radius and growing larger with a q of approximately 10%, the monolayer gradient could be reversed, either gradient could be repeated in order or alternating gradients that reverse the order of the nanoparticle layers could be constructed or multiple layers of each particle size could be used to construct the gradient. Moreover, chemically modified nanoparticles present the opportunity to add functionality to the nanostructure. The nanospheres may be solid and made of any number of polymers, metals, ceramics or other materials, so that the elastic properties and the interparticle forces may be varied. Hollow nanoparticles offer an interesting capability to insert voids, spheres shattered under compression by the shock wave, which would only act when the particles are compressed by sufficient force. Polymer nanoparticle shells may be constructed to carry other materials within the nanoparticle, providing the means to include in the structure indicators of the passage of a blast wave or the ability to release a beneficial agent to the users upon activation by the blast wave. The final product is a lightweight coating that does not change the flexibility of the treated material and can be made transparent by careful choice of nanoparticle materials. Taken as a whole, these characteristics of nanostructured gradient arrays provide a menu for the development of blast wave protection with targeted applications.

One version involves a structure that incorporates carbon allotrope (fullerene, nanotubes or graphene) and/or carbon allotrope-polymer composite layers into the overall structure. The carbon allotropes provide increased strength to the nanostructure since these materials rank among the strongest known. One embodiment employs “stacks” or “layers” of such structures with the carbon and/or carbon composites interspersed and defining the layer or stack limit. The effect, at each carbon interface, is to create a backward traveling wave causing attenuation of the incident shock wave, as well as a greatly reduced forward transmitted shock wave, which passes in to the next layer of the structure. A stack of 50 gradient nanoparticle structures (each composed of 30 nanoparticle layers) and composite layers would result in a 1 mm thick coating and significant attenuation of the incident shock wave. This structure would have a thickness of approximately 100 μm or 10 human hairs.

In one experimental embodiment, samples were made using a spin coating technique and measuring approximately 6 cm². Samples having a wide variety of gradients and employed solid polymer, solid silica, hollow polymer and filled (with long-chain hydrocarbons, as prototypes) silica nanoparticles were employed. Mono-dispersed coatings, tapered gradients (large to small and small to large) and repetitive gradients using polycarbonate substrates treated with UV light to make the surface polar were also used. Most samples employed a hexagonal close packed of the nanoparticles. The coatings typically had a tapered gradient of 320 nm/260 nm/220 nm/160 nm/130 nm. A laboratory-built impact tester was used to explore the effects of the nanostructures on the shock wave caused by the impact of a falling mass. The maximum in the impact shock wave was reduced in magnitude and delayed relative to initiation of the event. The reduced force was also spread over a greater temporal region to minimize the net effect. A list of some of our results is contained in the table below, along with brief descriptions of the nanosphere gradients.

The following table shows experimental impact shock results for polystyrene or silica nanospheres between two treated polycarbonate plates. The nanoparticles were solid spheres, except the 400 nm size, which were hollow:

Max. Width, Delay, Sample Force, N ms ms Comments Bare sensor 1334 0.16 — Control-no sample at all Polycarbonate 1156 0.27 0.10 Control-two x2 polycarbonate substrates #1 872 0.31 0.18 130-160-220-260: 8 repeats/4 layers #3 783 0.30 0.21 130-160-220-260-220- 160: 5 repeats/6 layers #5 623 0.34 0.22 130-160-220-260-320- 400-320-260-220-160: 3 repeats/10 layers #7 712 0.31 0.20 150-150-150 (silica): 30 repeats/1 layer #8 578 0.34 0.24 320-400: 13 repeats/2 layers #10  712 0.30 0.21 400-320-260-220-160- 130: 4 repeats/6 layers

The above described embodiments, while including the preferred embodiment and the best mode of the invention known to the inventor at the time of filing, are given as illustrative examples only. It will be readily appreciated that many deviations may be made from the specific embodiments disclosed in this specification without departing from the spirit and scope of the invention. Accordingly, the scope of the invention is to be determined by the claims below rather than being limited to the specifically described embodiments above.

-   -   The invention is: 

1. A composition comprising: a substrate, and a plurality of layers, each one of the plurality of layers including nanoparticle layers each including a plurality of nanoparticles arranged in a gradient array from smallest to largest, wherein the gradient array is tapered in multiple directions wherein the nanoparticles within at least one of the nanoparticle layers are unrestrained. wherein the diameters of the nanoparticles in each of the nanoparticle layers vary and the nanoparticle layers do not include carbon nanotubes, and carbon allotrope layers each including carbon allotrope members suspended in a matrix, and at least one of the carbon allotrope layers is between a first side of one of the nanoparticle layers and a second side of another one of the nanoparticle layers, and another at least one of the carbon allotrope layers is between one of the nanoparticle layers and the substrate, wherein the another at least one of the carbon allotrope layers abuts the substrate.
 2. The composition of claim 1, wherein at least one of the nanoparticles layers is hexagonal close packed.
 3. The composition of claim 1, wherein the nanoparticles in the nanoparticle layers comprise at least one of polymers, ceramics and metals.
 4. The composition of claim 1, wherein the nanoparticles of at least one layer of the nanoparticle layers includes at least one of solid nanoparticles, hollow nanoparticles, core-shell and filled core-shell particles.
 5. The composition of claim 1, wherein the carbon allotrope members include at least one chosen from a group which includes functionalized carbon nanotubes, functionalized graphene sheets and functionalized fullerenes.
 6. The composition of claim 1, wherein the allotrope members comprise carbon allotrope-polymer composites.
 7. The composition of claim 4, wherein the filled nanoparticles include at least one of a material or material systems which provide a means to include in the structure an indicator that the user has experienced a blast or shock wave sufficient to cause traumatic brain injury.
 8. The composition of claim 4, wherein the core shell particles and filled core shell particles are configured to deform and/or rupture by momentum transfer, destruction of special symmetry, restitution and interparticle and/or interlayer shear.
 9. The composition of claim 4, wherein the filled core shell particles can rupture introducing materials or materials systems into a blast environment to mitigate and/or remediate the effects of a blast wave.
 10. The composition of claim 4, wherein the filled core shell particles contain a beneficial agent released upon rupture of the filled core shell particles.
 11. A composite structure comprising: a substrate; nanoparticle layers each including nanoparticles, wherein the nanoparticles in each of the nanoparticles layers are arranged such that the nanoparticles with the largest diameter are concentrated towards a first side of the nanoparticle layer and the nanoparticles with smaller diameters are concentrated towards a second side of the nanoparticle layer, wherein the diameters of the nanoparticles in each of the layers vary by at least ten percent, and the nanoparticle layers do not include carbon nanotubes, and carbon allotrope layers each including carbon allotrope members suspended in a matrix, wherein at least one of the carbon allotrope layers is between a first side of one of the nanoparticle layers and a second side of another one of the nanoparticle layers, and wherein another at least one of the carbon allotrope layers is between one of the nanoparticle layers and the substrate, wherein the another at least one of the carbon allotrope layers abuts the substrate.
 12. The composite structure of claim 11, wherein at least one of the nanoparticle layers is hexagonal close packed.
 13. The composite structure of claim 11, wherein the nanoparticles of at least one layer of the nanoparticle layers include at least one of solid nanoparticles, hollow nanoparticles, core-shell and filled core-shell particles.
 14. The composite structure of claim 11, wherein the nanoparticles comprise at least one of polymers, ceramics or metals.
 15. The composite structure of claim 11, wherein the carbon allotrope members comprise carbon allotrope-polymer composites.
 16. The composite structure of claim 13, wherein the filled nanoparticles include at least one of a material or material systems which provide a means to include in the structure an indicator that the user has experienced a blast or shock wave sufficient to cause traumatic brain injury.
 17. The composite structure of claim 13, wherein the core shell particles and filled core shell particles are configured to deform and/or rupture by momentum transfer, destruction of special symmetry, restitution and interparticle and/or interlayer shear.
 18. The composite structure of claim 13, wherein the filled core shell particles are configured to rupture introducing materials or materials systems into a blast environment to mitigate and/or remediate the effects of a blast wave.
 19. The composite structure of claim 13, wherein the filled core shell particles contain a beneficial agent released upon rupture of the filled core shell particles.
 20. The composite structure of claim 13, wherein the carbon allotrope members are oriented parallel to at least one of the nanoparticle layers. 